Chromium containing mixed reactive azo dyestuffs



United States Patent 3,412,081 CHROMIUM CONTAINING MIXED REACTIVE AZODYESTUFFS Hans Ackermann, Riehen, Switzerland, assignor to J. R. GeigyA.G., Basel, Switzerland 3 No Drawing. Filed Oct. 5, 1964, Ser. No.401,639 Claims priority, application Switzerland, Oct. 7, 1963,12,301/63 7 Claims. (Cl. 260145) wherein A is a phenyl or a naphthylgroup with no reactive substituents, B is a phenyl or a naphthyl or apyrazolyl group with no reactive substituents, each O is ortho to N=N,and n is at most 3, is reacted with a metallizable disazo dyestutf ofthe formula wherein A is a sulfonated phenyl or a sulfonated naphthylgroup with no reactive substituents and no further ionogenicsubstituents, Z is a group containing a substituent which can split oilas :anion, and D can also contain lower alkyl or lower alkoxy, to formthe chromium-containing reactive azo dyestufi of the formula A -N=N-B(SOH) (3 o o Nil-z 110 s y A2N=N s which is useful in dyeing a widevariety of fibers. Since the dyeings are very deep, the new dyes areWell suited to attain full. black shades.

The :present invention concerns new chromium containing reactivedyestuffs, processes for the production thereof, their use for thedyeing of cellulose and polyamide material, as well as, as industrialproducts, the material dyed with the aid of these dyestuffs.

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Patented Nov. 19, 1968 It has now been found that valuable chromiumcontaining reactive dyestuifs are obtained by reacting a complexchromium compound of Formula I wherein:

A represents a radical of the benzene or naphthalene series containingno reactive groups,

B represents a radical of the benzene, naphthalene or pyrazole seriescontaining no reactive groups, each of A and B containing the oxygen Oin o-position to the azo bond, and

n represents a positive whole number of at most 3, with a metallisabledisazo dyestuif of Formula II OH HO Nil-Z A-N=N 301-! wherein:

A represents a sulphonated radical of the benzene or naphthalene seriescontaining no reactive groups, which radical contains no other ionogenicsubstituents apart from sulphonic acid groups,

Z represents a group which contains at least one substituent which canbe split off as anion, and

the benzene ring D can also contain lower alkyl and alkoxy groups toform a compound of Formula III A N N B I I ($0 K) o o n Cr o o NH z 6) QH N N A N D? ao s X III wherein A B and n have the meanings given inFormula I, and A Z and D have the meanings given in Formula II.

If A and B represent a radical of the naphthalene series then this isbound either in l-position to the azo group and in 2-position to O orvice versa.

If B is a radical of the pyrazole series then it is the radical of a1-aryl-, in particular lphenyl-3-methylpyrazole bound in the 4-positionto the azo group and in S-position to O.

If A is a radical of the naphthalene series, this can be a 1- as well asa Z-naphthyl radical. Preferably A is a sulphonated radical of thebenzene series containing no reactive groups, which radical contains noother ionogenic substituents apart from sulphonic acid groups.

The aromatic rings of B and A can contain the substituents usual in azodyestuffs as defined, for example lower alkyl groups such as the methylor ethyl group, lower alkoxy groups such as the methoxy or ethoxy group,halogens such as chlorine or bromine, sulphonic acid amide groups, loweralkylsulphonyl groups or the nitro group. The aromatic ring of Apreferably contains a sulphonic acid group and/or a nitro group.

In the benzene ring D, the radical A N=N preferably is in the p-positionto the hydroxyl group or to the oxygen atom O; otherwise the benzenering D is preferably not further substituted.

As substituents which can be split off as anion, the reactive group Zcontains mainly mobile halogen atoms, preferably chlorine, but alsobromine; or also sulphonic acid groups. The mobility of these atoms isdue to the presence of tertiary ring nitrogen atoms in heterocycles ofaromatic character, preferably G-membered heterocycles having at leasttwo tertiary ring nitrogen atoms.

Therefore Z is the radical of a cyclic imide halide of carbonic acid, inparticular a triazinyl radical containing at least one mobile halogenatom, e.g. a chloroor bromo-s-triazinyl radical which can contain asfurther substituents halogen, the primary or secondary amino group, analkoxy, alkylthio, phenoxy or phenylthio group, or an optionallycondensed diazinyl radical containing at least one mobile halogen atomwhich diazinyl radical is bound at a ring carbon atom preferablydirectly or by way of a CO-linkage, to the NH-group, e.g. a dichloro,dibromo, trichloro or tribromo pyrimidyl radical, the radical of the2,4-dichloropyrimidine-5- or 6-carboxylic acid or of the2,3dichloroquinoxaline-6-carboxylic acid; in particular Z is thetrichloro pyrimidyl radical.

The starting materials of Formulae I and II are known or can be producedby known methods. Thus, the chromium complexes of Formula I areobtained, for example, by reacting an agent giving off chromium with amonoazo dyestutf of Formula V in an acid medium. Azo dyestuffs ofFormula II are obtained, for example, by coupling a diazotised aminoazodyestuff of Formula VI with l-amin-8-hydroxy-3,6- or -4,6-disulphonicacid in an alkaline medium to form the aminodisazo dyestutf of FormulaVII on {II no Nli so a ' VII and reacting the latter with an acylatingagent introducing the radical Z. The halides of the carboxylic acidsmencases; generally however, it is necessary to evaporate the aqueoussolution to dryness in order to isolate the end product.

A modification of the process for the production of chromium containingreactive dyestuffs according to the invention consists in reacting achromium complex dyestufl of Formula IV A -N IN "E G) I I (50 1i) 0 o nCr o 0 m HQ d s A2-N=N 30 1! wherein A A B, D and n have the meaningsgiven in Formulae I or II, with an acylating agent introducing theradical Z to form a compound of Formula III, Whereby Z has the meaninggiven in Formula II.

The starting material of Formula IV is obtained, for example, byreacting a complex chromium compound of Formula I with an aminodisazodyestutf of Formula VII under the conditions described for the firstprocess.

The main acylating agents used to introduce the radical Z are thosementioned in the first process in the description of the production ofthe starting materials of Formula II.

The reaction of the amino dyestuff of Formula IV with the agentintroducing the radical Z is performed in the usual manner,advantageously in aqueous medium, if desired in the presence of inertorganic solvents which can easily be removed such as low aliphaticketones, e.g. acetone, and it is preferably performed in the presence ofmineral acid buffering agents such as sodium or potassium carbonate,sodium or potassium hydroxide solution, dior trisodium phosphate or diortri-potassium phosphate, sodium or potassium acetate or tertiarynitrogen bases such as pyridine.

The new chromium containing 2:1 complexes of Formula III are darkpowders. In the form of their alkali metal salts they dissolve well inwater. They dye cellulose material such as staple fibre, jute, ramie,hemp and, chiefly, cotton, as well as polyamide fibres, e.g. naturalpolyamide fibres such as wool and silk or synthetic polyamide fibressuch as nylon, in brown-black to green-black shades.

These materials are dyed with the dyestuffs according to the inventionby known methods.

The cellulose material is impregnated or printed, for

example at a low temperature such as 20-50 C., with the optioanallythickened dyestutf solution and the dyeing is then fixed by treatmentwith acid binding agents. Examples of acid binding agents are sodiumcarbonate, potassium carbonate, diand trisodium phosphate, sodiumhydroxide solution and, at temperatures of over 50 C., also potassium orsodium bicarbonate. The treatment with these agents can be performed atroom temperature or at a raised temperature. Instead of subjecting theimpregnated material to an alkaline after-treatment, in many cases theacid binding agent can also be added to the impregnating liquors orprinting pastes and then the dyeing is developed by short heating attemperatures over 100 C. to C. or by depositing for a longer time atroom temperature.

The new dyestuffs are bound chemically to the fibre by the treatmentwith acid binding agents. As the non-fixed part of the dyestuff is veryeasily washed out, the cellulose dyeings have excellent wet fastnessproperties after soaping.

Natural polyamide fibres are dyed in a hot, weakly acid, e.g. aceticacid, bath in the presence of auxiliaries which improve the eveness ofthe dyeing such as fatty acid/alkanolamine polycondensation products aswell as, optionally, in the presence of salts such as sodium chlo rideor sulphate. Synthetic polyamide fibres are advantageously dyed in ahotacid bath, then rinsed and aftert-reated in a boiling alkaline bath.

The dyestuffs according to the invention produce very deep dyeings and:are particularly well suited therefore to attain full black shades.

Further details can be seen from the following examples. Where nototherwise expressely st-ated, parts are given as parts by weight. Thetemperatures are in degrees centigrade. The relationship of parts byweight to parts by volume is as that of grams to cubic centimetres.

Example 1 and 88.6 parts of the disazo dyestufi? of the formula areadded to 400 parts of 80 hot water. The pH of the mixture is adjusted to6-6.5 by the addition of sodium hydroxide solution While stirring andthis pH is maintained until the completion of the reaction. Thetemperature is kept for the whole time at 80-850. The newly formeddyestuff is completely dissolved. After filtering oif slight impurities,the filtrate is concentrated to dryness in vacuo. A dark powder isobtained which easily dissolves in water.

If cotton is foularded at 30 with an 8% solution of this dyestutf whichsolution also contains 20 parts of sodium carbonate and 200 parts ofurea per litre, the impregnated goods are dried, then heated for 5minutes at 140 and finally soaped at the boilfor 30 minutes, then adeep, blueish black dyeing is obtained.

100 parts of wool are introduced at 50 in a dyebath consisting of 4000parts of water, 6 parts of this dyestuff, 6 parts of 30% acetic acid and1 part of a condensation product produced by condensing 2 mols ofdiethanolamine with 1 mol of coconut oil fatty acids, the temperature ofthe dyebath is then raised within 20 minutes to the boil, and the goodsare dyed at the boil for one hour and afterwards rinsed and dried. Adeep, blueish black wool dyeing is obtained.

g; If, instead of the 44.4 or 88.6 parts of the components given in theexample, equivalent amounts of the compounds given in columns H and IIIrespectively of the 9O3s N=N following Table I are used and theprocedure described in the example is followed, then dyestuffs havingsimillar properties and the shades given in column IV are obtained.

1 11 III W No. Chromium Complex DiaZO Dyestufi Shade 3 Cl OCr O SOaH l II I I 2 03s N=N-- -N=N OH N N Grecnlslr black. HO NH -o1 sonI I HOaS-$0311 (31 O Cr-O N/\N I I 3 N N I HO S N=NOH HO NH -01 Brown- N I lblack. (IJHS S0 11 N=N-- c1 9 s0 H038 SOaH 9 10 in the form of thesodium salt, are dissolved with a neu- 80-90 with equivalent parts ofthe metallisable disazo tral reaction in 700 parts of 80 hot water andthe solu dyestuif of the formula tion is reacted at this temperaturewith 23 parts of 2,4,5,6- tetrachloropyrirnidine. The pH is kept between5.5 and 6 by the dropwise addition of sodium hydroxide solution. 0H 0HOn completion of the reaction, the reaction mixture is I i I cooled to40, the reaction solution is clarified by filtration and the filtrate isconcentrated to dryness in vacuo. A dark powder is obtained whichdissolves very easily H013 S0311 in water.

The starting dyestufi for the above process is obtained Q- if the knownchromium complex compound of the formula SOSH N Oz I If cotton is paddyed with an 8% aqueous solution of the dystuff at 50 in the foulard,which solution contains also 5% of urea and 2% of soduim carbonate,dried at 0 80 and then steamed for 5-10 minutes and soaped at the boil,a deep black dyeing is obtained which is fast 0 Cr to washing.

Q9 Dyestuffs having similar properties are obtained if the chromiumcomplexes given in column II of the following Table II are reacted withthe acylating agents given in is reacted in a neutral or weakly alkalinesolution at column III at the temperatures shown in column IV.

I II III IV V No. Chromium Complex Acylating Agent Teinper- Shade a ure9 9 0-5 Blueish 01 01 F \//N\/ black.

HO S- N=N L li 2i 5 I \l 1 Cl 0 NH; 11

H0 8 SO H H03SN=l I 10 Same as N o. 9 above. 05 Blueish Cl C 0 Cl black.

11 N0 e 0-5 Bluefish r I N black.

01- C 0 Cl CH3 N 01 N=N- I O t I so n t I a HQ N=N L N- HO S- 50311 lSOaH I II III 1V V No. Chromium Complex Acylatlng Agent Tegiper- Shade12 blIOz '9 HOaS- S 11 N=N 0 1 0 Q 1 n1-c 0Q 01 Cr I Q 01 Cl Bil-90Greenish o 0 NH: black. I N N so H HO 0 H 01 I a I 3 3 SIO3H 13 Same asNo. 12 above. B -Br 80-90" Greenish black.

H038 N=N Cr N 01f TOCH; -30' Black. 0 0 NH: I 69 N N 01 s oarr 1103s S011 Nah I SOaH I claim: adjacent --O in o-position to the azo bond be- 1.A chromium-containing reactive dyestuif of the tween them, the latterbeing directly connected to formula a ring carbon atom of B,

n represents a positive whole number of at most 2, A represents a monoor'di-sulfonated radical of the a benzene or naphthalene series whichradical con- N N B tains sulfonic acid groups as sole ionogenic sub- 3stituents, and

Cr Z represents a member selected from the group con- 0 o mr- 6O sistingof 2,4-dichloro-s-triazinyl-, 2-ch'loro-4-amino- H C5 s-t riazinyl-,2-chloro-4-sulfopheny1amino-s-triazinyl-, N N 2-chloro-4-methoxy striazinyl-, 2,4,5-trichloro-pyrimidyl-, 2,4-dichloro pyrimidyl-,2,4-dibromo-py- 110 s rimidyland 2,4-dich1oro-pyrimidyl-carbonyl-, and AN=N 50 B any substituents of ring D other than those shown in whichcontains sulfonic acid groups as sole ionogenic substituents in themolecule thereof, and

wherein A represents the radical of an azo dyestutf component of thebenzene or naphthalene series (containing no reactive groups), Brepresents the radical of an azo dyestutf component of the benzene,naphthalene or l-phenyl-3-met'hyl pyrazole series, each of A and Bcontaining the the preceding formula being selected from the classconsisting of lower alkyl and lower alkoxy.

2. A chromium-containing reactive dyestufi as defined in claim 1,wherein the radical A -N=N is in the pposition to the oxygen --O- andthe benzene ring D contains no further substituents.

3. A chromium-containing reactive dyestuff as defined in claim 1,wherein Z represents the 2,4,5-trichloropyrimidyl radical.

4. A dyestuff he free acid form of which is of the formula l SOsH $1 INH @"ZZZIQQ Cl Cl SOaH 5. A dyestuff the free acid form of which is ofthe formula 14 6. A dyestufi? the free acid form of which is of theformula I I- 5 3} 5 "9 N=N-- O, l 3 0 0 l l H033 -N=N S aH 7. A dyestuffthe free acid form of which is of the formula HOsS 2N=N- 1' 0 0 NH N H-N=N c1 SOaH- S0311 H038 -N=N SOaH References Cited UNITED'STATESPATENTS 3,125,562 3/1964 Ammann et a1. 260- CHARLES B. PARKER, PrimaryExaminer.

JOSEPH P. BR-UST, D. M. PAP-UGA,

Assistant Examiners.

